CN111454470A - Modified aramid fiber and rubber composite material and preparation method thereof - Google Patents
Modified aramid fiber and rubber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified aramid fiber and rubber composite material and a preparation method thereof, wherein the preparation method comprises the following steps of a) modifying aramid fibers by using RF L impregnation liquid to obtain modified aramid fibers, b) placing the modified aramid fibers obtained in the step a) between rubber materials, and carrying out hot vulcanization to obtain the modified aramid fiber and rubber composite material.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a modified aramid fiber and rubber composite material and a preparation method thereof.
Background
The aramid fiber is an organic polymer fiber formed by connecting linear macromolecules formed by aromatic rings of amido bonds through a spinning process. The aramid fiber has a regular structure, and simultaneously has the advantages of high strength, high modulus, acid and alkali resistance, chemical reagent resistance, fatigue resistance, high temperature resistance, light weight, high wear resistance, rubber bonding performance and the like. With the mass production of aramid fibers, the aramid fibers not only replace steel wires, glass fibers and the like, but also replace the application of asbestos in many fields, and are widely applied to the fields of various rubber products, the building industry, aerospace, national defense construction and the like.
The aramid fiber has both the physical properties of inorganic fiber and the processing properties of organic fiber, can be compounded with general materials to endow the materials with special properties, and can be used as a framework material of composite materials such as reinforced plastics, rubber and the like. However, the aramid fiber has an obvious skin-core structure, a compact surface lattice, a highly crystalline molecular chain structure and a large steric hindrance effect, and is difficult to chemically react or otherwise act with other atoms or groups. Meanwhile, the surface of the aramid fiber lacks chemical active functional groups, the capability of forming hydrogen bonds is low, the surface wettability is poor, the high crystallinity of the fiber causes the surface to be smooth, the bonding performance with materials such as rubber is relatively poor, and the application of the aramid fiber in the field of rubber is greatly limited.
Disclosure of Invention
In view of the above, the present invention aims to provide a modified aramid fiber and rubber composite material and a preparation method thereof, and the modified aramid fiber and rubber composite material prepared by the preparation method provided by the present invention has strong interlayer adhesion, good integrity, excellent mechanical properties, and good water resistance, permeation resistance, oil resistance, viscoelasticity, and aging resistance.
The invention provides a preparation method of a modified aramid fiber and rubber composite material, which comprises the following steps:
a) modifying aramid fibers by using RF L impregnation liquid to obtain modified aramid fibers;
b) placing the modified aramid fiber obtained in the step a) between rubber materials, and carrying out hot vulcanization to obtain the modified aramid fiber and rubber composite material.
Preferably, the RF L impregnation solution in step a) comprises the following components:
45 wt% -50 wt% of RF solution;
40-43 wt% of butyl pyridine latex;
1-3 wt% of ammonia water;
the balance of water;
the RF solution comprises the following components:
23 to 30 parts of m-xylene;
32 to 40 parts by weight of formaldehyde;
5-10 parts by weight of sodium hydroxide;
480 to 520 parts by weight of water.
Preferably, the modification process in step a) is specifically:
soaking aramid fibers in the RF L impregnation liquid, stirring, taking out, and then washing and drying to obtain modified aramid fibers;
or the like, or, alternatively,
and spraying the aramid fiber by using the RF L impregnation liquid, and drying after the solvent is volatilized to obtain the modified aramid fiber.
Preferably, the rotation speed of the stirring is 300-400 rpm, and the time is 12-20 h.
Preferably, the drying temperature is 40-80 ℃.
Preferably, the rubber material in step b) is selected from BIIR rubber and/or NBR rubber; the number of layers of the rubber material is more than or equal to 2, and the thickness of each layer of the rubber material is 0.5-0.8 mm.
Preferably, the step b) of placing the modified aramid fiber obtained in the step a) between rubber materials specifically comprises the following steps:
the modified aramid fiber is respectively arranged between the adjacent BIIR rubber and between the adjacent BIIR rubber and NBR rubber.
Preferably, the temperature of the hot vulcanization in the step b) is 150-170 ℃, the pressure is 30-50 t, and the time is t90min～t100min。
The invention also provides a modified aramid fiber and rubber composite material prepared by the preparation method of the technical scheme.
The invention provides a modified aramid fiber and rubber composite material and a preparation method thereof, wherein the preparation method comprises the following steps of a) modifying aramid fibers by using RF L impregnation liquid to obtain modified aramid fibers, b) placing the modified aramid fibers obtained in the step a) between rubber materials, and carrying out heat vulcanization to obtain the modified aramid fiber and rubber composite material.
In addition, the preparation method provided by the invention can be realized by adopting a common rubber material sold in the market, the rubber material is not required to be modified, the difficulty of actual production is greatly reduced, and the preparation method is simple in process, easy to operate and suitable for large-scale production.
Drawings
Fig. 1 is an SEM image of aramid fibers in the aramid fiber cloth before modification in step (2) of example 1;
fig. 2 is an SEM image of aramid fibers in the aramid fiber cloth modified in step (2) of example 1;
FIG. 3 is a mechanical plot of the delamination of the composite layers of example 1 and comparative example 1;
FIG. 4 is a mechanical curve of the peeling of the modified aramid fiber from the BIIR rubber in the modified aramid fiber and BIIR-NBR rubber composite material provided in example 1 and comparative examples 2 to 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a modified aramid fiber and rubber composite material, which comprises the following steps:
a) modifying aramid fibers by using RF L impregnation liquid to obtain modified aramid fibers;
b) placing the modified aramid fiber obtained in the step a) between rubber materials, and carrying out hot vulcanization to obtain the modified aramid fiber and rubber composite material.
According to the invention, firstly, the aramid fiber is modified by using the RF L impregnation liquid to obtain the modified aramid fiber, and in the invention, the RF L impregnation liquid preferably comprises the following components:
45 wt% -50 wt% of RF solution;
40-43 wt% of butyl pyridine latex;
1-3 wt% of ammonia water;
the balance of water.
In the present invention, the RF solution preferably comprises the following components:
23 to 30 parts of m-xylene;
32 to 40 parts by weight of formaldehyde;
5-10 parts by weight of sodium hydroxide;
480-520 parts of water;
more preferably:
23 parts of m-xylene;
33 parts of formaldehyde;
6 parts by weight of sodium hydroxide;
482 parts of water.
The sources of the m-xylene, the formaldehyde and the sodium hydroxide are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used; the water may be deionized water as is well known to those skilled in the art. In the present invention, the preparation method of the RF solution is particularly preferably:
uniformly mixing m-xylene, formaldehyde, sodium hydroxide and water, and curing at 20-30 ℃ for 4-8 h to obtain an RF solution;
more preferably:
after m-xylene, formaldehyde, sodium hydroxide and water are uniformly mixed, the mixture is aged for 6 hours at 25 ℃ to obtain an RF solution.
In the present invention, the mass concentration of the buformin emulsion is preferably 35% to 45%, more preferably 41%, and the mass concentration of the ammonia water is preferably 25% to 30%, more preferably 28%.
Uniformly mixing the RF solution, the butyl pyridine latex, ammonia water and water, and curing at 20-30 ℃ for 16-24 h to obtain an RF L impregnation solution;
more preferably:
and uniformly mixing the RF solution, the butyl pyridine latex, ammonia water and water, and curing at 25 ℃ for 20 hours to obtain the RF L impregnation liquid.
In the present invention, the aramid fiber is preferably selected from aramid filament and aramid fiber plain cloth, unidirectional aramid fiber plain cloth, or aramid fiber twill cloth; the present invention is not particularly limited in this regard.
In the present invention, the modification process is preferably specifically:
soaking aramid fibers in the RF L impregnation liquid, stirring, taking out, and then washing and drying to obtain modified aramid fibers;
or the like, or, alternatively,
spraying aramid fiber by using an RF L impregnation liquid, and drying after a solvent is volatilized to obtain modified aramid fiber;
more preferably:
soaking aramid fibers in the RF L impregnation liquid, stirring, taking out, cleaning and drying to obtain the modified aramid fibers.
In the present invention, the rotation speed of the stirring is preferably 300rpm to 400rpm, more preferably 350 rpm; the stirring time is preferably 12 to 20 hours, and more preferably 16 hours.
In the present invention, the purpose of the cleaning is to rinse away residual accumulated RF L immersion fluid, using a clean water rinse well known to those skilled in the art.
In the present invention, the temperature for the drying is preferably 40 to 80 ℃, more preferably 60 ℃.
After the modified aramid fiber is obtained, the obtained modified aramid fiber is placed between rubber materials and is subjected to heat vulcanization to obtain the modified aramid fiber and rubber composite material. In the present invention, the rubber material is preferably selected from BIIR rubber and/or NBR rubber; the source of the rubber material is not particularly limited in the present invention, and commercially available or home-made compounded rubber products known to those skilled in the art may be used.
In the present invention, the number of layers of the rubber material is preferably 2 or more, more preferably 3; the thickness of each layer of the rubber material is preferably 0.5mm to 0.8 mm. Taking two layers of rubber materials as an example, the two layers of rubber materials can be selected from the same BIIR rubber or the same NBR rubber, or one layer is the BIIR rubber and the other layer is the NBR rubber.
In the invention, different types of rubber materials need to have similar vulcanization characteristics in the subsequent hot vulcanization process, namely, the rubber materials have the same t90 and t100 at the same vulcanization temperature or have the difference of less than 30s between the front and the back, so that the different types of rubber materials can be subjected to hot vulcanization in the same batch; the invention preferably adjusts the mixing formula of different rubber materials, when two or more rubber types exist in the composite material, the two or more rubbers are kept to have similar vulcanization characteristics under the same vulcanization condition.
In the invention, the adjustment mode of the mixing formula is preferably realized by adding a rubber additive; the rubber auxiliary agent preferably comprises one or more of a reinforcing filling system, a plasticizing system, a tackifying system, a vulcanizing system, an anti-aging system and a promoting system; wherein, the reinforcing filling system preferably adopts carbon black, such as N660, N330; the plasticizing system preferably employs an aromatic oil; the tackifying system preferably adopts titanium dioxide, such as HA100, and tackifying resin, such as SP1065, A250 and 964, and can increase the adhesive force between BIIR rubber and modified aramid fiber; the vulcanization system preferably employs sulfur, such as S-80; the anti-aging system (NBR rubber) is preferably an anti-aging agent such as 4020, since BIIR rubber is a saturated rubber and thus is not added; the accelerating system preferably adopts MgO, SA, ZnO, DM and CZ.
The method for mixing the rubber material is not particularly limited, and a mixing process known to those skilled in the art may be used. In order to ensure that the subsequent heat vulcanization compounding process can be realized, the sheet rubber material is preferably prepared by a mixing process; on the basis, the invention can randomly regulate and control the type and the size of the flaky composite material according to different use requirements, and is convenient for popularization and application.
In the invention, the process of placing the modified aramid fiber obtained in the step a) between rubber materials is preferably as follows:
the modified aramid fiber is respectively arranged between the adjacent BIIR rubber and between the adjacent BIIR rubber and NBR rubber. By adopting the process, the modified aramid fiber and the BIIR rubber and/or NBR rubber can be staggered and laminated in a multilayer sandwich structure; the above process can be realized by adopting a direct stacking or glue wiping process.
The apparatus for the hot vulcanization of the present invention is not particularly limited, and a press vulcanizer well known to those skilled in the art is used. In the present invention, the temperature of the hot vulcanization is preferably 150 ℃ to 170 ℃, more preferably 160 ℃; the pressure of the hot vulcanization is preferably 30 t-50 t, more preferably 35 t-45 t; the time of said hot vulcanization is preferably t90min～t100min, more preferably t90+5min。
The preparation method provided by the invention can be realized by adopting a common rubber material sold in the market, the rubber material is not required to be modified, the difficulty of actual production is greatly reduced, and the preparation method is simple in process, easy to operate and suitable for large-scale production.
The invention also provides a modified aramid fiber and rubber composite material prepared by the preparation method of the technical scheme. According to the preparation method provided by the invention, the aramid fiber is modified by selecting the specific modifier, a specific composite mode is combined, and the function of the aramid fiber as a framework material is fully exerted (the composite material is endowed with the properties of high strength, tear resistance, puncture resistance, cutting resistance, long service life and the like), so that the obtained modified aramid fiber and rubber composite material has strong interlayer bonding force, good integrity and excellent mechanical property; the product prepared by the preparation method can keep the inherent properties of the rubber material, including the good air tightness, permeability resistance, chemical solvent resistance and water resistance of BIIR rubber and the oil resistance and solvent resistance of NBR rubber, has good viscoelasticity and aging resistance on the whole, can be used as a special material and a military material, can be particularly used as a storage device used for a long time in severe environments such as seawater and the like, and has wide application prospect.
The invention provides a modified aramid fiber and rubber composite material and a preparation method thereof, wherein the preparation method comprises the following steps of a) modifying aramid fibers by using RF L impregnation liquid to obtain modified aramid fibers, b) placing the modified aramid fibers obtained in the step a) between rubber materials, and carrying out heat vulcanization to obtain the modified aramid fiber and rubber composite material.
In addition, the preparation method provided by the invention can be realized by adopting a common rubber material sold in the market, the rubber material is not required to be modified, the difficulty of actual production is greatly reduced, and the preparation method is simple in process, easy to operate and suitable for large-scale production.
To further illustrate the present invention, the following examples are provided for illustration.
Example 1
(1) Preparing an RF L impregnation liquid:
the RF L dip was prepared according to the formulation and conditions of table 1 at room temperature.
Table 1 formulation and conditions for preparing RF L dip in example 1
(2) And (2) dipping the aramid fiber cloth with the area of 20cm × 20cm into the RF L dipping solution prepared in the step (1), reacting for 16h under mechanical stirring at 350rpm, taking out the aramid fiber cloth, washing away residual gathered RF L dipping solution with clear water, and drying at 60 ℃ to constant weight to obtain the modified aramid fiber cloth.
(3) Mixing BIIR:
the mixing formula of BIIR is as follows: 100 parts of BIIR, 8 parts of carbon black N66060, 7 parts of naphthenic oil, 7 parts of titanium dioxide (HA-100), 54 parts of tackifying resin SP-106, 78 parts of MgO-750.2, 2 parts of stearic acid, 801.25 parts of ZnO-801.25, 0.625 part of sulfur (S-80) and 752 parts of thiazole vulcanization accelerator DM-752; the filling factor was 85%.
The mixing process of BIIR comprises the following steps: one-stage mixing (60 ℃, 60 rpm): adding BIIR, titanium dioxide (HA-100) and MgO-75 in 0 min; half of carbon black N660 is added in 1 min; adding the other half of carbon black N660, tackifying resin SP-1065, naphthenic oil and stearic acid after 3 min; cleaning for 5 min; and (4) discharging the rubber within 7min (considering two factors of temperature and time, and if the temperature is raised to 145 ℃, discharging the rubber as soon as possible so as to avoid debromination). Two-stage kneading (50 ℃, 40 rpm): adding a section of master batch, ZnO-80, sulfur (S-80) and DM-75 in 0 min; 3min rubber discharging, discharging pieces with the size of 0.5mm from an open mill, standing at room temperature for 24h to obtain the mixed BIIR rubber.
Mixing NBR:
the mixing formula of the NBR is as follows: 100 parts of NBR, 805 parts of ZnO, 2 parts of SA 2, 40202 parts of anti-aging agent, 33040 parts of carbon black N, 2 parts of sulfur accelerator CZ, 2 parts of sulfur (S-80), 2 parts of A250 resin and 2 parts of 964 resin; the filling factor was 85%.
The mixing process of the NBR comprises the following steps: one-stage mixing (60 ℃, 60 rpm): adding NBR for 0 min; adding ZnO-80, SA, an anti-aging agent 4020, A250 resin and half of carbon black N330 for 2 min; adding the other half of carbon black N330 in 5 min; cleaning for 7 min; discharging rubber for 10min, and discharging pieces with the roller spacing of 0.3mm by an open mill; adding sulfur (S-80), 964 resin and CZ (2min, 60 ℃, the roll speed of 20rpm front and back is 1.1: 1), discharging the rubber sheet with the thickness of 0.5mm, and standing at room temperature for 24h to obtain the mixed NBR rubber.
(4) Respectively cutting the mixed BIIR rubber, NBR rubber and modified aramid fiber cloth into sample pieces of 150mm × 100mm, and mixing the sample pieces with BIIR rubber-modified aramid fiber cloth-BIIR rubber-modified aramid fiber clothLay-up of structures of Velcro-NBR rubber at 160 ℃ of × t90+5And vulcanizing at min × 40t (a flat vulcanizing machine) to obtain the modified aramid fiber and BIIR-NBR rubber composite material.
Comparative example 1
The preparation process provided in example 1 was used with the difference that: directly adopting the unmodified aramid fiber cloth in the step (2) to replace the modified aramid fiber cloth in the step (4); obtaining the aramid fiber and BIIR-NBR rubber composite material.
The morphology of the aramid fibers in the aramid fiber cloth before and after modification in the step (2) of example 1 is characterized, and an SEM image is shown in figures 1-2; as can be seen from a comparison of fig. 1 and 2, the surface of the aramid fiber is rough after modification, and the surface layer has the modifier adhered thereto.
Further testing the bonding force between the aramid fiber in the composite material and the BIIR rubber and NBR rubber respectively (peeling off the composite material by using a universal tensile machine at a speed of 500 mm/min), and the results are shown in FIG. 3; as can be seen from fig. 3, the adhesion between the modified aramid fiber cloth and the rubber is much higher than that between the unmodified aramid fiber cloth and the rubber; wherein, the bonding force of the modified aramid fiber cloth and the BIIR rubber is 2.74 times of that of the unmodified aramid fiber cloth, and the bonding force of the modified aramid fiber cloth and the NBR rubber is 1.5 times of that of the unmodified aramid fiber cloth. Therefore, the BIIR rubber and the modified aramid fiber cloth in the modified aramid fiber and BIIR-NBR rubber composite material provided by the embodiment 1 of the invention have very high bonding force, and the BIIR rubber in the inner layer plays a bonding role between the modified aramid fiber cloth, so that the integrity is good.
The modified aramid fiber and BIIR-NBR rubber composite provided in example 1 of the present invention was tested for various properties, and the results are shown in table 2.
TABLE 2 data of various properties of the modified aramid fiber and BIIR-NBR rubber composite material provided in example 1 of the present invention
Note: the NBR-aramid cloth composite material and the BIIR-aramid cloth composite material are respectively soaked in crude oil and seawater at 60 ℃ for 15 d.
As can be seen from table 2, the modified aramid fiber provided in example 1 of the present invention and the BIIR-NBR rubber composite material have excellent mechanical properties as a whole, the BIIR rubber on the outer layer provides the composite material with water resistance and permeation resistance, the NBR rubber on the other side provides the composite material with oil resistance, and the composite material has good viscoelasticity as a whole and excellent aging resistance.
Comparative example 2
The preparation method provided by the embodiment 1 is adopted, and the difference is that the dopamine aqueous solution is adopted to replace the RF L impregnation liquid in the step (2) to modify the aramid fiber cloth to obtain modified aramid fiber cloth, and further the modified aramid fiber and BIIR-NBR rubber composite material is obtained;
the preparation method of the dopamine aqueous solution specifically comprises the following steps:
measuring 1200m L deionized water at room temperature, accurately weighing 3.71g DA-HCl (dopamine hydrochloride, MDA-HCl (189.64), MDA (153.18)) and adding into deionized water, stirring with a glass rod until completely dissolved, adding 4g Tris-HCl, stirring uniformly, and adding NH3·H2Adjusting the pH value to 8.5 by O, and aging for 30min to obtain a dopamine aqueous solution with the mass concentration of DA of 2.5 g/L.
Comparative example 3
The preparation method provided by the embodiment 1 is adopted, and the difference is that the ethanol solution of the silane coupling agent Si-69 is adopted to replace the RF L impregnation liquid in the step (2) to modify the aramid fiber cloth to obtain modified aramid fiber cloth, and further obtain a modified aramid fiber and BIIR-NBR rubber composite material;
the preparation method of the ethanol solution of the silane coupling agent Si-69 specifically comprises the following steps:
at room temperature, 1080m of L anhydrous ethanol and 120m of L silane coupling agent Si-69 are taken and mixed evenly under the mechanical stirring of 300rpm, and ethanol solution of the silane coupling agent Si-69 is obtained.
As shown in FIG. 4, the modified aramid fiber cloth modified by different modifiers has certain effect on improving the bonding performance between the BIIR rubber and the modified aramid fiber, but the modification effect of DA and the modification effect of the silane coupling agent Si-69 are not as good as those of the RF L impregnation liquid, especially the modification effect of the silane coupling agent Si-69 is the worst.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a modified aramid fiber and rubber composite material comprises the following steps:
a) modifying aramid fibers by using RF L impregnation liquid to obtain modified aramid fibers;
b) placing the modified aramid fiber obtained in the step a) between rubber materials, and carrying out hot vulcanization to obtain the modified aramid fiber and rubber composite material.
2. The method of claim 1, wherein the RF L immersion fluid in step a) comprises the following components:
45 wt% -50 wt% of RF solution;
40-43 wt% of butyl pyridine latex;
1-3 wt% of ammonia water;
the balance of water;
the RF solution comprises the following components:
23 to 30 parts of m-xylene;
32 to 40 parts by weight of formaldehyde;
5-10 parts by weight of sodium hydroxide;
480 to 520 parts by weight of water.
3. The preparation method according to claim 1, wherein the modification in step a) is specifically performed by:
soaking aramid fibers in the RF L impregnation liquid, stirring, taking out, and then washing and drying to obtain modified aramid fibers;
or the like, or, alternatively,
and spraying the aramid fiber by using the RF L impregnation liquid, and drying after the solvent is volatilized to obtain the modified aramid fiber.
4. The method according to claim 3, wherein the stirring is performed at a rotation speed of 300 to 400rpm for 12 to 20 hours.
5. The method according to claim 3, wherein the drying temperature is 40 to 80 ℃.
6. The method according to claim 1, wherein the rubber material in step b) is selected from BIIR rubber and/or NBR rubber; the number of layers of the rubber material is more than or equal to 2, and the thickness of each layer of the rubber material is 0.5-0.8 mm.
7. The preparation method of claim 6, wherein the step b) of placing the modified aramid fiber obtained in the step a) between rubber materials is specifically as follows:
the modified aramid fiber is respectively arranged between the adjacent BIIR rubber and between the adjacent BIIR rubber and NBR rubber.
8. The process according to claim 1, wherein the hot vulcanization in step b) is carried out at a temperature of 150 ℃ to 170 ℃ and at a pressure of 30t to 50t for a time t90min～t100min。
9. A modified aramid fiber and rubber composite material, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
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| CN117552145A (en) * | 2024-01-04 | 2024-02-13 | 昆山东利新材料科技有限公司 | Tire regenerated environment-friendly fabric and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583857A (en) * | 2004-06-09 | 2005-02-23 | 华南理工大学 | Preparing method for Fanglun-rubber composite materials |
| CN106501174A (en) * | 2016-11-03 | 2017-03-15 | 常熟理工学院 | The double interface shear strength method of testings of RFL surface treatment aramid fiber rubber composites |
| CN109403040A (en) * | 2018-01-16 | 2019-03-01 | 烟台泰和工程材料有限公司 | A kind of preparation of aramid fiber modified solution |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583857A (en) * | 2004-06-09 | 2005-02-23 | 华南理工大学 | Preparing method for Fanglun-rubber composite materials |
| CN106501174A (en) * | 2016-11-03 | 2017-03-15 | 常熟理工学院 | The double interface shear strength method of testings of RFL surface treatment aramid fiber rubber composites |
| CN109403040A (en) * | 2018-01-16 | 2019-03-01 | 烟台泰和工程材料有限公司 | A kind of preparation of aramid fiber modified solution |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117552145A (en) * | 2024-01-04 | 2024-02-13 | 昆山东利新材料科技有限公司 | Tire regenerated environment-friendly fabric and preparation method thereof |
| CN117552145B (en) * | 2024-01-04 | 2024-04-02 | 昆山东利新材料科技有限公司 | Tire regenerated environment-friendly fabric and preparation method thereof |
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